CN102441410A - Catalyst for storing hydrogen by organic matter carrier and preparation method of catalyst - Google Patents
Catalyst for storing hydrogen by organic matter carrier and preparation method of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for storing hydrogen by an organic matter carrier and a preparation method of the catalyst. The catalyst comprises the following components in percent by weight: 0.15-5 percent of metal active component, 0.1-4 percent of additive, 2-5 percent of adhesive and the balance of carrier. The carrier containing a rare earth metal is prepared by adopting a hydrothermal reaction and then immersed in an active metal water solution, then dried and roasted, and then mixed with the adhesive to obtain the catalyst. Compared with the prior art, the catalyst has the characteristics of proper acid strength, high reaction activity, good selectivity and the like; and the rare earth metal is added, the dispersion degree of the active metal can be increased, surface carbon deposit of the catalyst is reduced, thus the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to dehydrogenation of a kind of petroleum hydrocarbon product and preparation method thereof, especially relate to a kind of Catalysts and its preparation method that is used for organic matter carrier storage hydrogen.
Background technology
Hydrogen Energy is the important develop energy of the world today, and it possibly replace existing energy and material gasoline and diesel oil, and will on every field, bring into play crucial effect.Because hydrogen has features such as inflammable, easy diffusion and light weight, safe, the efficient and dead-tight loss during people will pay the utmost attention to storing hydrogen in actual applications and transport.
O.S ultan in 1975 and M.S haw propose to utilize the conception of aqueous chemical hydrogen carrier storage hydrogen capable of circulation first.This technology is that a pair of reversible reaction by hydrogen storing agents such as some alkene, alkynes or aromatic hydrocarbon and hydrogen realizes hydrogenation and dehydrogenation.Invertibity and hydrogen storage content equal angles from reaction; Benzene and toluene are more satisfactory organic liquid hydrogen storing agents; Cyclohexane (cyclo-hexane is called for short Cy) and hexahydrotoluene (methyl cyclo hexane is called for short MCH) are comparatively ideal organic liquid hydrogen carriers.Organic liquid hydride is reversible to store the circulatory system that hydrogen system is a sealing, is made up of 3 processes such as dehydrogenation reaction of storage, transportation and the hydrogen carrier of the hydrogenation reaction of hydrogen storing agent, hydrogen carrier.Utilize the catalytic hydrogenation device, with storing hydrogen in hydrogen carriers such as Cy or MCH.Because hydrogen carrier is liquid condition under normal temperature, normal pressure, its storage and transport simple.After hydrogen carrier is transported to the destination, again through the catalytic dehydrogenation device, under the effect of dehydrogenation, discharge the Hydrogen Energy that is stored, supply the user to use, hydrogen storing agent is storage after supercooling, transportation, cycling and reutilization then.
Storing up hydrogen storage methods such as hydrogen, hydride hydrogen-storing, high pressure compressed Chu Qing with traditional cryogenic liquefying compares; The organic liquid hydride hydrogen storage has following characteristics (Okada Y; Imagawa K; Agi FY, Asaoka S.Unimodalporous spinel and its application to a new catalyst material.Studies in Surface Scienceand Catalysis 2003; 145:431):
(1) hydrogen storage content is big, hydrogen-storage density is high.The theoretical hydrogen storage content of benzene and toluene is respectively 7.2% and 6.2% (mass fraction), is higher than the hydrogen storage content of existing hydride hydrogen-storing and high pressure compressed storage hydrogen, and its hydrogen-storage density is also respectively up to 56.0g/L and 47.4g/L.
(2) the storage hydrogen efficiency is high.The closed cycle system that constitutes with Cy storage hydrogen is an example, and the efficient of the recuperable words whole circulation of liberated heat process is up to 98% when supposing benzene hydrogenation.
(3) hydrogen carrier storage, transportation and maintenance safe are convenient, and storage hydrogen facility is easy, are particularly suitable for length and carry apart from Hydrogen Energy.Hydrogen carrier Cy and MCH at room temperature are in a liquid state, and be similar with gasoline, can utilize existing storage and transporting equipment easily, and this carries significant to long distance, extensive Hydrogen Energy.
(4) it is reversible to add the dehydrogenation reaction height, and hydrogen storing agent can recycle repeatedly.
The dehydrogenation of organic liquid hydrogen carrier is a strong heat absorption, highly reversible reaction.Want to improve dehydrogenation efficient, must the rising reaction temperature or reduce the pressure of reaction system, especially under all maybe the harsh conditions of time dependent unstable state operation with the non-hydrogen of car hydrogen supply and temperature, inlet amount, coking deactivation very easily.But it is satisfactory that high temperature active, stability and the low-temperature dehydrogenation activity of existing catalyst also are difficult to.So can the dehydrogenation system of organic liquid hydrogen carrier one of key in application property problem is to develop efficient cryogenic, long-life dehydrogenation.
(Li such as the Chen Jinfu of University of Petroleum
2O is to Pt-Sn/C-Al
2O
3The influence [J] of catalyst surface acidity and MCH dehydrogenation. solar energy journal, 2002,23 (6): the 782-786.) Pt-Sn-K/ γ-Al of use modification
2O
3Catalyst, at 400 ℃, 0.12MPa, air speed 6h
-1, to react under the reaction condition of pure MCH charging, result's demonstration improves 2 times at least than activity before the modification, but stability can only remain on about 100h.
People such as AliJK (Patricio Reyes.Chem Tech Biotechnol, 2003,64:233-240.) once at 573～673K, 1～2MPa, liquid air speed 12h
-1, Pr/ γ-Al
2O
3Do under the experiment condition of catalyst, the film that this 2mm is thick when having investigated the MCH dehydrogenation is to the separating effect of hydrogen, and its conversion ratio has improved more than 4 times.But the Pd-Ag film also exists some problems, like Pd-Ag membrane reactor poor stability, and the heat supply difficulty, and also the easy knot of diaphragm seal is fast, and to easy poisonings such as sulphur and chlorine, the life-span is short, costs an arm and a leg etc.
Patricio Reyes and El Nabarawy (Powerful H
2Supply from organic hydride and itscirculation system for hydrogen transportation [J] .Catalyst&Catalysis2005; 47 (2): find that 137-9.) exploitation nanoscale dehydrogenation improves dispersion degree of active components, is expected to obtain the catalyst of low-temperature dehydrogenation excellent performance.Experimental result shows, in the time of 300 ℃ homemade nanometer dehydrogenation to the conversion rate of dehydrogenation of MCH than Pt-Sn-K/ γ-Al
2O
3Improved nearly 30%.(University of Petroleum's journal (natural science edition), 1995,19 (4): 103-107.) prepared novel γ-Al such as Su Junya
2O
3(CarbonCovered Alumina CCA), discovers that the dehydrogenation hydrogen activity of Ni/CCA and stability all are superior to Ni/ γ-Al to carbon covered carrier
2O
3CCA is γ-Al
2O
3Advantage such as the active mutually and high mechanical properties of the high metal of carrier and active carbon specific area height, anti-carbon deposit, anti-nitride poison the strong speciality of ability and combine, and help improving dispersion degree of active components, improve the anti-coking performance of catalyst.
Japan Association of Industrial Technology Research Institute and the supercritical fluid (Applied expand But, look で ki ru Supercritical Carbon Dioxide Fluid を shi ta use plain water preservation organic materials [J]. Industrial Materials ,2005.01.01:1 -4) developed together with Supercritical CO
2 as solvent, Rh / γ-Al
2 O
3 as a catalyst for hydrogen production method combined process.With above-mentioned compared with techniques, have that reaction temperature is low, conversion ratio is high, selectivity is good and as the CO of solvent
2Can recycling etc. characteristics, be a new method that prolongs catalyst life, reduces environmental pollution.(pressure 6.0～9.0MPa), runnability is poor continuously but this reaction pair equipment requirements is high.
Organic liquid hydride hydrogen storage technology is used for motor vehicle fuel, is H
2-O
2The research of fuel cell power generation has also obtained bigger progress.Countries such as Switzerland, Canada and the Britain research of this respect of just throwing oneself at present; Switzerland has developed two generations experiment type hydrogen powered vehicle; Road performance test shows: it is fully feasible technically that this hydrogen storage system is used for motor vehicle fuel; But also exist under non-hydrogen, unstable state operation, desorption temperature is higher, conversion rate of dehydrogenation is on the low side, the serious problems of the easy inactivation of catalyst.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of Catalysts and its preparation method that is used for organic matter carrier storage hydrogen with higher conversion ratio, reaction stability and anti-carbon property to be provided.
The object of the invention can be realized through following technical scheme:
A kind of catalyst that is used for organic matter carrier storage hydrogen is characterized in that this catalyst comprises following component and weight percentage:
Metal active constituent 0.15～5;
Auxiliary agent 0.1～4;
Adhesive 2～5;
The carrier surplus.
Preferred 0.5～the 3wt% of described metal active constituent content, the preferred 0.5～2wt% of auxiliary agent content.
Preferred 1.5～the 3wt% of described metal active constituent content, the preferred 1～2wt% of auxiliary agent content.
Described metal active constituent is an amorphous state, and metal active constituent is selected from one or more among Pt, Pd, Ru, Rh or the Ag.
Described auxiliary agent is a rare earth metal.
Described adhesive is an aluminium oxide.
Described carrier comprises SBA-15 zeolite, SBA-16 zeolite or MCM-22 zeolite, preferred MCM-22 zeolite.
A kind of Preparation of catalysts method that is used for organic matter carrier storage hydrogen is characterized in that this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight percent content:
Metal active constituent 0.15～5,
Auxiliary agent 0.1～4,
Adhesive 2～5,
The carrier surplus;
(2) the carrier immersion is contained in rare-earth metal chloride or the nitrate aqueous solution, drop goes out behind the dipping 6h, after 100～120 ℃ of following dryings, obtains containing the carrier of rare earth metal again through 400～500 ℃ of roastings;
The carrier that (3) will contain rare earth metal immerses and to contain in reactive metal chloride or the nitrate aqueous solution, and drop goes out behind the dipping 12h, behind 100～120 ℃ of down dry 3～6h, puts into round-bottomed flask and feeds nitrogen, dropwise adds KBH
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves subsequent use again;
(4) product that step (3) is obtained is with after adhesive mixes, and pinching is molded, dry through mixing, obtain being used for the catalyst that the organic matter carrier stores up hydrogen after the roasting.
Described carrier is bar shaped, annular, wheel shape, clover or bunge bedstraw herb shape.
The pH value of described reactive metal chloride or nitrate aqueous solution is 3～5.
Compared with prior art, the present invention has the following advantages:
(1) the present invention uses mesoporous material to be carrier, especially uses the MCM-22 zeolite molecular sieve to be carrier, has two separate mutual disconnected duct systems, is made up of regular ten-ring, twelve-ring duct and supercage.The MCM-22 zeolite is compared than the mesopore molecular sieve of other type; B acid and L acid are stronger relatively; There is bigger hole in its surface; Structural characteristics, high microporosity and pore volume and good hydrothermal stability and acid performance cause the MCM-22 zeolite that reactions such as alkylation, aromatisation, toluene disproportionation are all had excellent catalytic performance;
(2) there is interaction between rare earth element and the reactive metal material, promotes the dispersion of reactive metal, make metal fining.Because itself storage oxygen performance when improving dehydrogenation activity, can also reduce the catalyst surface carbon deposit, improve the catalyst high temperature stability performance on the other hand, prolong catalyst service life.
Description of drawings
Fig. 1 is for being the XRD figure of the catalyst of carrier with SBA-15;
Fig. 2 is for being the XRD figure of the catalyst of carrier with SAPO-41;
Fig. 3 is for being the XRD figure of the catalyst of carrier with SAPO-11;
Fig. 4 is for being the XRD figure of the catalyst of carrier with MCM-22.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Use raw material source and specification:
SBA-15, SBA-16, MCM-41, MCM-22, MCM-49, SAPO-11, SAPO-41 are provided by the farsighted bright Chemical Industry Science Co., Ltd in Shanghai.Agents useful for same in the instance except that specifying, is chemically pure reagent.
Select for use the GC-7890II gas chromatograph to carry out toluene and MCH Determination on content.Chromatographic condition is: 95 ℃ of post oven temperature, degree, and 135 ℃ of injector temperature, 135 ℃ of fid detector temperature, raw material and major-minor product are by interior mark calibration curve standard measure.
The dehydrogenation rate is calculated by following formula:
The catalyst activity appreciation condition:
By mass ratio is MCH: Pt=10: 1 amount joins 2.5g MCH in the catalyst system and catalyzing, under normal pressure, nitrogen atmosphere, stir and rise to gradually reaction temperature required (1 ℃/min).Each temperature spot is measured, and the reaction time is 1h.
Embodiment 1
(skeleton in) SBA-15, SBA-16, MCM-41, MCM-22, MCM-49, SAPO-11, the SAPO-41 that will contain rare earth metal immerses respectively and contains that (the pH value should be controlled at 3 in the reactive metal chloroplatinic acid; Platinum content 3.0%); Flood that drop goes out after 12 hours; After under 100 ℃ dry 6 hours, put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.The XRD figure of catalyst that with SBA-15 is carrier is as shown in Figure 1.
Embodiment 2
(skeleton in) SBA-15, SBA-16, MCM-41, MCM-22, MCM-49, SAPO-11, the SAPO-41 that will contain rare earth metal immerse respectively contain the reactive metal palladium bichloride or nitrate aqueous solution in (the pH value should be controlled between 4; Palladium content 3.0%); Flood that drop goes out after 12 hours; After under 120 ℃ dry 3 hours, put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.The XRD figure of catalyst that with SAPO-41 is carrier is as shown in Figure 2.
Embodiment 3
(skeleton in) SBA-15, SBA-16, MCM-41, MCM-22, MCM-49, SAPO-11, the SAPO-41 that will contain rare earth metal immerses respectively that (the pH value should be controlled at 3 in the aqueous solution that contains the reactive metal ruthenic chloride; Ruthenium content 3.0%); Flood that drop goes out after 12 hours; After under 110 ℃ dry 4 hours, put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.The XRD figure of catalyst that with SAPO-11 is carrier is as shown in Figure 3.
Embodiment 4
(skeleton in) SBA-15, SBA-16, MCM-41, MCM-22, MCM-49, SAPO-11, the SAPO-41 that will contain rare earth metal immerses respectively that (the pH value should be controlled between 4 in the aqueous solution that contains the reactive metal radium chloride; Rhodium content 3.0%); Flood that drop goes out after 12 hours; After under 110 ℃ dry 4 hours, put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.
Embodiment 5
(skeleton outer) MCM-22 that will contain rare earth metal immerses that (the pH value should be controlled at 3 in the aqueous solution that contains the reactive metal ruthenic chloride; Ruthenium content 3.0%), floods that drop goes out after 12 hours, at 100 ℃ down after dry 5 hours; Put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.
Embodiment 6
(skeleton outer) MCM-22 that will contain rare earth metal immerses that (the pH value should be controlled between 4 in the aqueous solution that contains the reactive metal ruthenic chloride; Ruthenium content 2.5%), floods that drop goes out after 12 hours, at 120 ℃ down after dry 5 hours; Put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.The XRD figure of catalyst that with MCM-22 is carrier is as shown in Figure 4.
Embodiment 7
(skeleton outer) MCM-22 that will contain rare earth metal immerses that (the pH value should be controlled between 3～4 in the aqueous solution that contains the reactive metal ruthenic chloride; Ruthenium content 1.5%), floods that drop goes out after 12 hours, at 100 ℃ down after dry 5 hours; Put into round-bottomed flask and feed nitrogen, dropwise add the KBH of metering
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.
Embodiment 8
MCM-22 is immersed in the aqueous solution contain the reactive metal ruthenic chloride (pH value should be controlled at 4, ruthenium content 3.0%), flood that drop goes out after 12 hours,, put into round-bottomed flask and feed nitrogen, dropwise the KBH that measures of adding at 100 ℃ down after dry 6 hours
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves again.
Embodiment 9
A kind of Preparation of catalysts method that is used for organic matter carrier storage hydrogen, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight percent content:
Amorphous metal Pt active component 0.15wt%, rare earth metal auxiliary agent 0.1wt%, alumina adhesive 2wt%, surplus are that the SBA-15 zeolite molecular sieve of bar shaped is as carrier;
(2) immersion of SBA-15 zeolite molecular sieve is contained in the aqueous solution of rare-earth metal chloride, drop goes out behind the dipping 6h, after 100 ℃ of following dryings, obtains containing the SBA-15 zeolite molecular sieve of rare earth metal again through 400 ℃ of roastings;
The SBA-15 zeolite molecular sieve that (3) will contain rare earth metal immerses and to contain in the aqueous chloride solution of Pt, and the pH value of this solution is 3, and drop goes out behind the dipping 12h, behind 100 ℃ times dry 6h, puts into round-bottomed flask and feeds nitrogen, dropwise adds KBH
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves subsequent use again;
(4) product that step (3) is obtained is with after the adhesive aluminium oxide mixes, and pinching is molded, dry through mixing, obtain being used for the catalyst that the organic matter carrier stores up hydrogen after the roasting.
Embodiment 10
A kind of Preparation of catalysts method that is used for organic matter carrier storage hydrogen, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight percent content:
Amorphous metal Pd active component 3wt%, rare earth metal auxiliary agent 2wt%, alumina adhesive 3wt%, surplus be the annular the MCM-22 zeolite molecular sieve as carrier;
(2) immersion of MCM-22 zeolite molecular sieve carrier is contained in the nitrate aqueous solution of rare earth metal, drop goes out behind the dipping 6h, after 120 ℃ of following dryings, obtains containing the carrier of rare earth metal again through 500 ℃ of roastings;
The carrier that (3) will contain rare earth metal immerses and to contain in the nitrate aqueous solution of reactive metal Pd, and the pH value of this solution is 4, and drop goes out behind the dipping 12h, behind 120 ℃ times dry 3h, puts into round-bottomed flask and feeds nitrogen, dropwise adds KBH
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves subsequent use again;
(4) product that step (3) is obtained is with after adhesive mixes, and pinching is molded, dry through mixing, obtain being used for the catalyst that the organic matter carrier stores up hydrogen after the roasting.
Embodiment 11
A kind of Preparation of catalysts method that is used for organic matter carrier storage hydrogen, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight percent content:
Amorphous metal Ru active component 5wt%, rare earth metal auxiliary agent 4wt%, alumina adhesive 5wt%, surplus are that the MCM-22 zeolite molecular sieve of wheel shape is as carrier;
(2) immersion of MCM-22 zeolite molecular sieve carrier is contained in the rare earth metal nitrate aqueous solution, the pH value of this solution is 5, and drop goes out behind the dipping 6h, after 120 ℃ of following dryings, obtains containing the carrier of rare earth metal again through 500 ℃ of roastings;
The carrier that (3) will contain rare earth metal immerses and to contain in reactive metal chloride or the nitrate aqueous solution, and drop goes out behind the dipping 12h, at 110 ℃ down behind the dry 5h, puts into round-bottomed flask and feeds nitrogen, dropwise adds KBH
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves subsequent use again;
(4) product that step (3) is obtained is with after adhesive mixes, and pinching is molded, dry through mixing, obtain being used for the catalyst that the organic matter carrier stores up hydrogen after the roasting.
Claims (10)
1. one kind is used for the catalyst that the organic matter carrier stores up hydrogen, it is characterized in that this catalyst comprises following component and weight percentage:
Metal active constituent 0.15～5;
Auxiliary agent 0.1～4;
Adhesive 2～5;
The carrier surplus.
2. a kind of catalyst that is used for organic matter carrier storage hydrogen according to claim 1 is characterized in that the preferred 0.5～3wt% of described metal active constituent content, the preferred 0.5～2wt% of auxiliary agent content.
3. a kind of catalyst that is used for organic matter carrier storage hydrogen according to claim 1 is characterized in that the preferred 1.5～3wt% of described metal active constituent content, the preferred 1～2wt% of auxiliary agent content.
4. a kind of catalyst that is used for organic matter carrier storage hydrogen according to claim 1 is characterized in that described metal active constituent is an amorphous state, and metal active constituent is selected from one or more among Pt, Pd, Ru, Rh or the Ag.
5. a kind of catalyst that is used for organic matter carrier storage hydrogen according to claim 1 is characterized in that described auxiliary agent is a rare earth metal.
6. a kind of catalyst that is used for organic matter carrier storage hydrogen according to claim 1 is characterized in that described adhesive is an aluminium oxide.
7. a kind of catalyst that is used for organic matter carrier storage hydrogen according to claim 1 is characterized in that described carrier comprises SBA-15 zeolite, SBA-16 zeolite or MCM-22 zeolite.
8. Preparation of catalysts method that is used for organic matter carrier storage hydrogen as claimed in claim 1 is characterized in that this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight percent content:
Metal active constituent 0.15～5,
Auxiliary agent 0.1～4,
Adhesive 2～5,
The carrier surplus;
(2) the carrier immersion is contained in rare-earth metal chloride or the nitrate aqueous solution, drop goes out behind the dipping 6h, after 100～120 ℃ of following dryings, obtains containing the carrier of rare earth metal again through 400～500 ℃ of roastings;
The carrier that (3) will contain rare earth metal immerses and to contain in reactive metal chloride or the nitrate aqueous solution, and drop goes out behind the dipping 12h, behind 100～120 ℃ of down dry 3～6h, puts into round-bottomed flask and feeds nitrogen, dropwise adds KBH
4-KOH solution reduction no longer includes in system till the gas release, behind the distilled water cyclic washing, puts into absolute ethyl alcohol and preserves subsequent use again;
(4) product that step (3) is obtained is with after adhesive mixes, and pinching is molded, dry through mixing, obtain being used for the catalyst that the organic matter carrier stores up hydrogen after the roasting.
9. a kind of Preparation of catalysts method that is used for organic matter carrier storage hydrogen according to claim 8 is characterized in that described carrier is bar shaped, annular, wheel shape, clover or bunge bedstraw herb shape.
10. a kind of Preparation of catalysts method that is used for organic matter carrier storage hydrogen according to claim 8 is characterized in that the pH value of described reactive metal chloride or nitrate aqueous solution is 3～5.
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| CN106378180A (en) * | 2016-10-28 | 2017-02-08 | 姚光纯 | Method for preparing catalyst by steeping active component into target material in targeting manner |
| CN107537560A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Dehydrogenation, preparation method and its application method |
| CN109701588A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Dehydrogenation and preparation method thereof |
| CN109701529A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | High dispersive dehydrogenation, preparation method and application method |
| CN109701532A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Cover charcoal dehydrogenation, preparation method and its usage |
| CN114751373A (en) * | 2022-04-15 | 2022-07-15 | 山东大学 | Mechanical catalysis method for preparing hydrogen and carbon by cracking methane |
| CN114939436A (en) * | 2022-05-17 | 2022-08-26 | 中山大学 | Preparation method of Pd nano-particle porous composite material and application of Pd nano-particle porous composite material in low-temperature and normal-temperature hydrogen storage |
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